1. ICEM’ 11– Reims France 26 Septembre 2011 Presented by: Albert A. Kruger Glass Scientist Supervisor, Vitrification Group of the DOE WTP Project Office Engineering Division High Waste Loading Glass Formulations for Hanford High-Aluminum HLW Streams wP - 59388

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3. 3 July 2011

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5. 5 Generation of Hanford Tank Wastes 9 Reactors; 4 Fuel Reprocessing Flowsheets; 100,000 MT Fuel Processed

6. In Fiscal Year 2007, ORP initiated a testing program to develop and characterize HLW & LAW glasses with higher waste loadings, and where possible higher throughput, to meet the processing and product quality requirements. This effort spans the investigation of the melt dynamics and cold cap properties to vitrification processes at the conditions close to those that exist in continuous waste glass melters. 6 Glass Formulation for HLW & LAW Treatment

7. Background: Current estimates indicate that the number of HLW canisters to be produced in the WTP is 13,500 (equivalent to 40,500 MT glass). The ca. 50,000 MT of sodium to be processed into glass equates to 588,000 tons of ILAW glass. The current glass formulation efforts have been conservative in terms of achievable waste loadings. These formulations have been specified to ensure the glasses are homogenous, preclude secondary phases (sulfate-based salts or crystalline phases), are processable in joule-heated, ceramic-lined melters and meet WTP Contract terms. 7 Glass Formulation for Waste Treatment

8. 8 WTP Flow Sheet - Key Process Flows LAW Vitrification (90+% of waste mass) HLW Vitrification (90+% of waste activity) Pretreatment (solid/liquid separation – Cs, Sr, TRU removal) SLUDGE SUPERNATANT Maximize Mass Maximize Activity Hanford Tank Waste

9. 9 It is likely that the capacity of the HLW vitrification plant can be increased significantly by implementation of a variety of low-risk, high-probability changes, either separately or in combination. These changes include: Operating at the higher processing rates demonstrated at the HLW pilot melter Increasing the glass waste loading in HLW glasses for wastes that are challenged by Al, Al plus Na, Bi, and Cr. Operating the melter at a slightly higher temperature

10. 10 Melter Scale Comparison WTP High Level Waste 3.75 m 2 West Valley 2.2 m 2 Savannah River DWPF-SRS 2.4 m 2 WTP Low Activity Waste RPP-LAW 10 m 2 EnergySolutions M-Area Mixed Waste DM-5000 5m 2 LAW Pilot DM-3300 3.3 m 2 Hanford HLW Pilot DM-1200 1.2 m 2 EnergySolutions/VSL Test Melters DM-100 0.11 m 2 EnergySolutions/VSL Test Melters DM-10 0.02 m 2

11. 11 Oxide Compositions of Limiting Waste Streams (wt%) Waste Component Bi LimitedCr LimitedAl Limited Al and Na Limited Al 2 O 3 22.45%25.53%49.21%43.30% B2O3B2O3 0.58%0.53%0.39%0.74% CaO1.61%2.47%2.21%1.47% Fe 2 O 3 13.40%13.13%12.11%5.71% Li 2 O0.31%0.36%0.35%0.15% MgO0.82%0.16%0.24%0.44% Na 2 O12.97%20.09%7.35%25.79% SiO 2 12.04%10.56%10.05%6.22% TiO 2 0.30%0.01%0.02%0.35% ZnO0.31%0.25%0.17%0.36% ZrO 2 0.40%0.11%0.81%0.25% SO 3 0.91%1.52%0.41%0.44% Bi 2 O 3 12.91%7.29%2.35% ThO 2 0.25%0.04%0.37%0.04% Cr 2 O 3 1.00%3.07%1.07%1.44% K2OK2O0.89%0.37%0.29%1.34% U3O8U3O8 3.48%7.59%7.25%4.58% BaO0.02%0.03%0.11%0.06% CdO0.00%0.01%0.05%0.02% NiO3.71%1.06%0.82%0.20% PbO0.48% 0.84%0.18% P2O5P2O5 9.60%3.34%2.16%4.10% F-1.58%2.00%1.37%0.46% Total100.00%

12. These approaches successfully demonstrated increases in glass production rates and significant increases in waste loading at the nominal melter operating temperature of 1150° C. Results of this work have demonstrated the feasibility of increases in waste-loading from about 25 wt% to 33-55 wt% (based on oxide loading) in the glass, depending on the waste stream. Results of this work have resulted in IHLW glasses with waste loadings at 50 wt% (with >25 wt% Al2O3); and Glass throughput rates in excess of 3x commissioning targets. 12

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14. 14 Glass Formulation for HLW Treatment Reduction in HLW Canister Count 70% 62%48% 59%

15. 15 Composition and Properties of Aluminum Limited Waste and Glass Formulation HWI-Al-19 with 45% Waste Loading (wt%) - Al-Limited Waste * Waste in Glass Glass Forming Additives Target Glass HWI-Al-19 Al 2 O 3 53.2723.97- B2O3B2O3 0.420.1919.0019.19 BaO0.120.05- Bi 2 O 3 2.541.14- CaO2.391.084.505.58 CdO0.050.02- Cr 2 O 3 1.160.52 F1.480.67- Fe 2 O 3 13.115.90- K2OK2O0.310.14- Li 2 O0.380.173.403.57 MgO0.260.12- Na 2 O7.963.586.009.58 NiO0.890.40- P2O5P2O5 2.341.05- PbO0.910.41- SO 3 0.440.20- SiO 2 10.884.9022.1027.00 TiO 2 0.020.01- ZnO0.180.08- ZrO 2 0.880.39- Sum100.045.055.0100.0 * Renormalized after removal of radioactive components

16. 16 Composition and Properties of Aluminum Limited Waste and Glass Formulation HWI-Al-19 with 45% Waste Loading (wt%) Cont’d Viscosity @1150ºC, P 33 Conductivity @1150ºC, S/cm 0.27 Crystal Content, As Melted None Crystal Content, 72 hr at 950 o C 1.3 Crystal Content, CCC 1.9 TCLP Pass PCT, g/L -DWPF-EAHWI-Al-19- B16.70.654B Li9.60.794Li Na13.30.624Na -DWPF-EAHWI-Al-19- - Empty data field

17. 17 Composition of LAW Waste Stream and Contributions to Melter Feed and Product Glass UFP-VSL-00062A Contract Run UF Permeate Tank: 9,400 Data Points for Liquids Amount required to replace 6 wt% Na2O in 100 kg glass ComponentsUnits Bulk Average MolesGrams Oxides in Glass (wt%) Na + mol/kg water4.43193.54452Na 2 O - 6.00 Al(OH) 4 mol/kg water0.2711.9322Al 2 O 3 - 0.61 Na + mol/mol Al16.23--- - OHmol/mol Al10.22121.92072- NO 3 mol/mol Al2.9134.72152- - NO 2 mol/mol Al0.769.1417- -2 PO 4 mol/mol Al0.182.1204P 2 O 5 - 0.15 -2 SO 4 mol/mol Al0.141.7160SO 3 - 0.13 wt% water%79.7-43690 Total 534696.89 - Empty data field

18. 18 Compositions (wt%) and Properties of Aluminum-Limited Waste and Glass Formulation HWI-Al-19LW with 45% HLW Waste Loading Oxides Al-Limited Waste* HLW Oxides in Glass LAW Oxides in Glass Glass Forming Additives in Glass Target Glass HWI-Al-19LW Al 2 O 3 53.27%23.97%0.61% —#—# 24.58% B2O3B2O3 0.42%0.19%—19.00%19.19% BaO0.12%0.05%—— Bi 2 O 3 2.54%1.14%—— CaO2.39%1.08%—3.61%4.69% CdO0.05%0.02%—— Cr 2 O 3 1.16%0.52%—— F1.48%0.67%—— Fe 2 O 3 13.11%5.90%—— K2OK2O0.31%0.14%—— Li 2 O0.38%0.17%—3.40%3.57% MgO0.26%0.12%—— Na 2 O7.96%3.58%6.00%—9.58% NiO0.89%0.40%—— P2O5P2O5 2.34%1.05%0.15%—1.20% PbO0.91%0.41%—— SO 3 0.44%0.20%0.13%—0.33% SiO 2 10.88%4.90%—22.10%27.00% TiO 2 0.02%0.01%—— ZnO0.18%0.08%—— ZrO 2 0.88%0.39%—— TOTAL100.0%45.0%6.89%48.11%100.0% Renormalized from after removal of radioactive components. # — indicates empty data field.

19. 19 Compositions (wt%) and Properties of Aluminum-Limited Waste and Glass Formulation HWI-Al-19LW with 45% HLW Waste Loading Cont’d Viscosity @ 1150°C, P34.51 Electrical Conductivity @ 1150°C, S/cm0.245 Crystal Content, 70 hrs at 950°C 1.7% (Spinel) Crystal Content, CCC 2.9% (Spinel)

20. 20 Composition of LAW Waste Stream and Contributions to Melter Feed and Product Glass UFP-VSL-00062A Contract Run UF Permeate Tank: 9,400 Data Points for Liquids Amount required to replace 6 wt% Na2O in 100 kg glass ComponentsUnits Bulk Average MolesGrams Oxides in Glass (wt%) Na + mol/kg water4.43193.54452Na 2 O - 6.00 Al(OH) 4 mol/kg water0.2711.9322Al 2 O 3 - 0.61 Na + mol/mol Al16.23--- - OHmol/mol Al10.22121.92072- NO 3 mol/mol Al2.9134.72152- - NO 2 mol/mol Al0.769.1417- -2 PO 4 mol/mol Al0.182.1204P 2 O 5 - 0.15 -2 SO 4 mol/mol Al0.141.7160SO 3 - 0.13 wt% water%79.7-43690 Total 534696.89 - Empty data field

21. 21 Waste loading increased to 50 wt% (26.6 wt% Al 2 O 3 ); And Glass production rate further increased Most recent tests have reached 3000 kg/m 2 /d WTP Baseline Requirement Formulation Improvements Glass Production Rate, kg/m 2 /d 2500 2000 1500 1000 500

22. 22 Questions?

23. 23 Backup Information

24. 24 How is the Vitrified Waste Dispositioned? High-Level Waste Canisters 2’ x 14.75’ (0.61 x 4.5 m) 6,600 pounds of glass 600 canisters to be produced/year Temporarily stored at Hanford until National Repository opened Low-Activity Waste Containers 4’ x 7.5’ (1.22 x 2.286 m) 13,000 pounds of glass 1,300 containers to be produced/year Disposed on Hanford Site